TW448475B - Wet cleaning apparatus - Google Patents

Abstract

A kind of wet cleaning apparatus is provided, in which the wet cleaning apparatus has the capability of removing the extreme minute amount of impurities such as heavy metal and colloidal materials contained in ultrapure water that is used as rinsing water in the cleaning process of a semiconductor and thereby for inhibiting the adhesion of impurities on a substrate such as fine particles and heavy metal that adversely affect the characteristics of a device. A wet cleaning apparatus, wherein the ultrapure water is fed to the use point within the apparatus through a pipeline such that rinsing is carried out by using ultrapure water as the rinsing water, has the following features: A module is disposed at a midpoint of the pipeline within the apparatus in which the module is filled with the porous membrane that holds the polymer chains having the cation-exchange group, the anion-exchange group, or the chelating group within the porous membrane.

Description

4484 75 V. Description of the invention (l) --- The present invention relates to a cleaning device for preventing the adhesion of extremely small amounts of impurities, especially metals, in pure water during the wafer cleaning process in the semiconductor industry. Japanese Patent Application Laid-Open No. 8_89954 discloses that in order to reduce impurities such as heavy metals immediately before use, a polymer chain having a cation exchange group, an anion exchange group, and a chelate-forming group is filled and maintained immediately before use ^ An ion absorbing membrane with a mean pore diameter of 0.01 to 1 m (hereinafter referred to as a cation absorbing membrane, an anion absorbing membrane, and a chelating membrane, and these three are collectively referred to as an ion absorbing membrane). The module is imported. · &Quot; The hollow wire membrane module system having a cation exchange group is suitable for the removal of metals', especially the removal of alkali metals and alkaline earth metals is good. The hollow wire membrane module system having an anion exchange group can efficiently remove particles and colloidal substances. The hollow wire membrane module system having a cation exchange group has a function of removing heavy metals to an extremely low concentration. I know that by using hydrogen-added ultrapure water, it is possible to suppress particles from adhering to broken substrates or to remove particles that have adhered. Also, Japanese Patent Application Laid-Open No. Q 10713 discloses that wafers are treated with ultra-pure water containing hydrogen or hydrogen and rare gases, which greatly improves the removal rate of hydrocarbons, and that the hydrogen end of the substrate can be easily implemented. Due to the extremely high removal rate of hydrocarbons with hydrogen-added ultrapure water, it should be available in the case of cleaning with hydrogen-added ultrapure water compared to the case of cleaning with ultra-pure water without hydrogen. Cleaner wafer surface. However, if the comparison is based on the use of hydrogen-purified ultrapure water for cleaning

Page 5 4484 7 5 V. Description of the invention (2) ------- The film on the silicon substrate (for example, an insulating film such as a gate insulating film) and an ultra-pure water formed without adding hydrogen. In the case where cleaning is performed, the inventors of the present invention found that the quality of the film (for example, pressure resistance) of the former film is inferior to that of the latter film. To find out the reason, although the addition of hydrogen ultrapure water has the effect of removing particles and preventing the particles from adhering to the substrate, I know that it has the effect of easily attaching metal impurities to the substrate. This is clearly explained as the cause of deterioration of the film quality (for example, deterioration of the insulation withstand voltage). ^ The purpose of the invention is to provide a wet cleaning device, which can remove a very small amount of impurities such as metal and colloidal impurities contained in ultrapure water used as cleaning water in the semiconductor cleaning process, and suppress the use of the device. Adhesion of impurities such as fine particles, heavy metals, and the like that have deteriorated to the substrate surface. [Summary of the Invention] The wet cleaning device of the present invention supplies ultrapure water to a use point inside the device through piping, and performs cleaning by using ultrapure water as a washing liquid. The internal piping is provided with a module in the middle, and the above-mentioned mop is filled with a porous membrane that holds a polymer bond having an anion exchange group, a cation cross-linkage, or a chelate-forming group inside the membrane. 66 八 ίSecond two cleaning device is a multi-tank or single-tank water two & cleaning device or each piece of cleaning device used to perform wet cleaning, in wet cleaning, based on ultra-pure: To clean the wafer surface, and then use ultrapure water to clean the bell = medicine on the surface 'and finally dry the wafer surface. It also includes a washing-type device that sprays super water. Among them, the cleaning device also includes a wet bench. Wetness

4484 75____ V. Description of the invention (3) Machines are equipped with cleaning facilities for exhaust equipment ’These are cleaning equipment with pipes for supplying ultrapure water or liquid chemicals and pipes for discharging washing liquid or washing water. 'Ultra-pure water produced by ultra-pure water systems often circulates the main circuit and draws the necessary amount from the main circuit through branch piping' as dilution water or washing water for the liquid necessary for washing. μ Branch piping is introduced into the washing device or fishing machine, and the total ultrapure water is supplied according to the different washing processes. Among them, the purpose of the final cleaning, which is the final process of the cleaning process, is to remove the attached medicine from the substrate of the semiconductor being cleaned by cleaning. Among them, the final cleaning refers to washing with ultrapure water or adding ultrapure water to the crystals before the IPA (2 propanol) vapor drying, spin drying, or Marangoni drying. Medicines with round surface. Since the cleaning by ultrapure water does not have the effect of suppressing the adhesion of impurities such as metals, it is necessary to remove extremely small amounts of impurities with washing water after washing with a chemical solution. : Different from the final process of fishing and washing, the dilute gas acid solution is used to etch the surface to expose the bare broken surface where the oxide film does not exist, and then the ultra pure water washing process is performed slightly. -Signed in ΐ Ϊ Ϊ The purpose of washing with pure water is to remove the medicines with 酸 acid by washing with ultrapure water, but impurities such as metals are temporarily stored in the "## occasion" because the silicon surface is exposed, so Attachment of impurities. When impurities are attached to the substrate, ultrapure water is completely removed. Attachment: In its red, ultrapure water used for final cleaning is required to be completely free of easily adherent substances on the substrate surface. Impurities such as metals.

Page 7 4484 75 Description of the 5th invention (4) Reduction of impurities, especially metals, in ultrapure water 'Even if an inductively coupled plasma mass spectrometer (ICP-MS) is used, a highly sensitive machine analysis device It is also difficult to detect. The presence of impurities at a level below the lower limit of quantification of the analysis machine 'is deduced to cause the impurities to adhere to the substrate surface. The metals present in ultrapure water are almost almost cations, but we can infer that the cations alone do not exist, but form a weak electrostatic bond with negatively charged silica (si 1 i ca) or organic matter, and then cluster or There is gelatinization. Therefore, the device for removing metal impurities in the so-called ultrapure water system of ion exchange or reverse osmosis is difficult to remove the weakly-charged and small-sized grouped substances 'so I know that these metal impurities also exist at the outlet of ultrapure water' And attached to the substrate surface. Among them, from the research of the inventors of the present invention, it is known that by using a module that fills an ion absorbing film that holds a polymer chain having an anion exchange group, a cation exchange group, or a chelate-forming group, it is possible to remove the conventional Impurities such as grouped metals that cannot be removed by the system. Among them, the ion-adsorbing membrane used in the present invention is, for example, a hollow linear porous membrane holding a polymer chain having an ion-exchange group inside the membrane, and 1 g of a membrane base having an ion exchange of 0.2 to 10 milliequivalents can also be used. Hollow linear porous membrane with an average pore diameter of 0.01 ~ 1 μm. The manufacturing method and the like are described in detail in Japanese Patent Application Laid-Open No. 8_89954. Anion absorbing membrane systems, for example, those who have a 4th grade amine as the exchange group, generally those who use gas methyl benzyl ethylene to be 4th grade 'can also use pyridine or flavor 4484 7 5 V. Description of the invention (5) azole The other heteroatoms are graded 4th. The cation absorbing film system uses a sulfonic acid group, a phosphoric acid carboxyl group, or the like as the exchange group. The chelate-forming system uses iminoacetic acid, hydrogenthio, and ethylenediamine as exchange groups. The cleaning method used in semiconductor manufacturing has conventionally used a method called RCA cleaning as shown in Figure 1 ^ This RCA cleaning is based on argon peroxide and mixed with acid or alkali. It is characterized by washing at warm temperature, and the ultra-pure water washing process is repeated after the medicine is washed. + The function of ultra pure water cleaning is nothing more than removing the medicines used in the substrate. In the cleaning process, impurities other than the chemical liquid can hardly be removed. Therefore, it is necessary to supply purified ultra pure water. Especially in the final cleaning, if pollution occurs, it is necessary to re-perform the entire cleaning process, so it is necessary to consider recontamination. In order to improve the water quality of the ultrapure water used in the final cleaning, the plasma adsorption membrane module is incorporated into the ultrapure water piping for the final cleaning in the cleaning device, which can be used for wet cleaning. The problem of poor cleaning. To provide a cleaning device for the purpose of 'characteristics: For example, in the case of washing Shi Xijing in order to manufacture semiconductors, the first clean process "2 hydrogenation ultrapure water" is first filled with Inside the membrane, a module that has an anion ::: base exchange, cation exchange base, or chelate-forming polymer chain is used to handle the ultrapure water, and then add hydrogen. Nitrogen-added ultrapure water has the ability to remove particles attached to the substrate

Page 9 4484 75 V. Description of the invention (6) and occasions to prevent fine particles from adhering to the substrate 'If it is easy to be attached to the substrate, it will be reduced if it exists in the super knowledge' It is also possible to use hydrogen-added ultrapure water. Therefore, the present invention is Not only qualitative attachment. Therefore, it can also be formed on the substrate by washing after the hair. Therefore, a method of cleaning is invented and a module of an ion-adsorbing film is invented for processing, and after adding impurities, hydrogen is added. In addition, for example, in a cleaning process for manufacturing a semi-wet cleaning process, after adding pure water ', a module filled with an ion exchange group or a chelate-forming group in the membrane is used to process the membrane. For example, in order to manufacture semi-conductors filled with an ion-exchange membrane that maintains an anion-exchanged polymer chain, it is used to clean metal ions in the house or exist in ultrapure water. However, there are substances around the metal. Approaching and grouping, and further changing the charge by the metal stone or organic acid, has an effect, but there are problems with metal impurities. Metal impurities in pure water can prevent metal from adhering to the substrate. By suppressing fine particles, it is also possible to suppress a metallic cleaning seat cleaning device, and even if an insulation film having a high insulation withstand voltage is applied, for example. The device 'is characterized in that when silicon wafers are cleaned by filling them with metal conductors sufficiently reduced by ultrapure water, in the case of hydrogen ultrapure water, it is possible to maintain an anion-exchange group when adding hydrogen to the super portion, When the silicon wafer is cleaned by ion exchange of the polymer chain of the exchange base, at least two or more of the base, the cation exchange base, or the chelation module can be used to form a pipe of a wet machine. The metal itself is ionized into a colloidal state with negative charges such as stone stone or organic acid. Element-type, or by paired Shi Xi, which cannot be completely removed by a membrane module

4484 7 5 V. Description of the invention (7) Occasion, and at this time, it is possible to introduce a different exchange-based membrane ’by the renter ’s violation of Putian Group 〇

Remove metal completely. The combination of the two types of Satoshi J ^ ^ membranes is as follows: • Cationic adsorption membrane + anion adsorption membrane • Chelation membrane + anion adsorption anion adsorption membrane + cationic adsorption membrane anion adsorption Membrane + Chelate Film 'Cationic Adsorption Film + Chelate Film Integration Film Cationic adsorption film and the combination of the two types of films is as follows: cation adsorption film + chelation film + anion adsorption film chelation film + cation adsorption Implantation + Anion Adsorption Membrane Cationic Adsorption Membrane + Anion Adsorption Membrane + Anion Adsorption Membrane + Anion Adsorption Membrane + Anion Adsorption Membrane Anion Adsorption Membrane + Adsorption Membrane + Anion Adsorption Membrane The combination of an anion absorbing membrane and a cation absorbing membrane containing chelated hydrazone is best used for the removal of impurities. The addition of hydrogen to ultrapure water can also be performed upstream of the module, and can also be performed downstream of the module. Implementation upstream can effectively prevent the metal from adhering to the substrate. In the case of hydrogen-containing ultrapure water, there are not only cases where argon is added, but also cases where hydrogen is included from the beginning of production. [Brief Description of the Drawings] Fig. 1 is a flowchart showing a washing sequence. Figure 2 shows the sound of the cleaning system used in the first embodiment. 'Page 11 4484 7 5 V. Description of the invention (8) Figure 3 shows the schematic diagram of the cleaning system used in the fourth embodiment. . Fig. 4 is a schematic view showing a cleaning system used in the tenth embodiment. Fig. 5 is a schematic view showing a cleaning system used in the fifteenth embodiment. [Explanation of symbols] 1, Z, 3, 4, 5 ~ washing tank; 6 ~ ozone generator; 7 ~ ultrapure water piping; 8 ~ mixing tank; 9 ~ mixing tank; 10, 12 ~ metering of fluoric acid 11 ~ hydrogen light tank; 13 ~ piping; 19 ~ hydrogen dissolving membrane module; 20, 21, 22 ~ ion adsorption module. [Best Mode for Carrying Out the Invention] In the examples, a cation absorbing film, an anion absorbing film, and a chelate film were used as the ion absorbing film. This plasma absorbing film was produced by the method described in Hori et al., Journal of Membrane Science 132 (1997) 203 211. An ammonium-type ion chain anion sorption membrane is structured by introducing a hollow linear ion-exchange group into a polymer chain of aerosol and fixed by a cation-absorbing membrane system which is introduced into a stiff ethylene by a hollow-wire ion exchange group and fixed . Porous membrane surface with copolymerization of strongly basic 4-based styrene and stilbene ° > Porous membrane surface with high-strength chelate membrane of copolymer of strong acid cycle = stupid ethylene on hollow wire porous membrane 矣The surface of the polymer has a high score for introducing an iminodiacetic acid group to an alkyl propyl acryl acrylate and a tau copolymer of ethylene.

4484 75 V. Description of the invention (9) The structure in which the sub-chain is fixed. (Embodiment 1) Fig. 2 shows a room-temperature wet cleaning device 'which is composed of five processes and has a cleaning tank 5 in the cleaning machine. The cleaning tank 1 was cleaned with ozone ultrapure water, and the cleaning tank 2 was added with a surfactant in a mixed solution of hydrofluoric acid and hydrogen peroxide, and the ultrasonic wave was cleaned. In the washing tank 3, washing with ozone ultrapure water is performed, while in the washing tank 4, a dilute acid treatment is performed, and in the washing tank 5, the final ultrapure water washing is performed. In the cleaning tank 丨 and the cleaning tank 3, ultrapure water is supplied from the ultrapure water pipe 7 and the ozone generated by the ozone generator 6 is supplied through the pipe 13 to be mixed and dissolved in the pipe to become ozone ultrapure. Water is supplied to the washing tank. 0 β is provided with a mixing tank 8 in the cleaning tank 2, and the necessary and necessary medicines are supplied to the mixing tank from a tank 10 containing an interfacial active fluoric acid and a measuring tank of hydrogen peroxide ii. The tank 8 ′ and the finished medicine are transferred from the cleaning tank 8 to the cleaning tank 2. A mixing tank 9 is provided in the washing tank 4, and appropriate and necessary medicines are supplied to the mixing tank 9 from the metering tank 12 of fluoric acid. The medicines having been completely mixed are transferred from the washing tank 9 to the washing tank 4. In the washing tank 5 (at the use point for final washing), ultrapure water is supplied from the ultrapure water distribution 7, and the dissolved oxygen concentration in this ultrapure water is 2 Ag / L. Branch piping inside the washing machine that supplies ultrapure water to the washing tank 5

Page 13 4484 7 5

In filtration, an anion absorbing membrane mold is introduced between the supply outlet of the washing tank, and the module 20 is used to filter the entire amount and the 0.1 " m particle removal membrane group is used as an ion absorbing membrane module. 20 Ultra-pure water is introduced into the cleaning tank. First, the crystal surface manufactured by the 8-inch diameter pulling method (cz) is η-type (100) and the impedance is 8 ~ 12Ω. The wafer is cleaned from the ozone ultrapure water in the cleaning tank 1 to the thin cleaning in the cleaning tank 4. Next, the washing time of the ultrapure water performed in the washing tank 5 is changed by ^ 0 minutes, 1 day, 3 days, and 7 days, and the washing is performed. After the washing was completed, the Shixi wafer was dried, and the total amount of copper, iron, and nickel, the so-called metal impurities 77 in the attached impurities were measured by a total reflection glare X-ray analysis device, and the results are shown in Table 1.

4484 75 V. Description of the invention (11) (Table υ Attached to broken crystal §) of copper (unit: X109atom / cm2) Molybdenum m fine-grained before washing 1 t lower limit ατ lower t lower limit 1 lower lower α Example 2: J? • lower limit ατ set 1 ΓτΙΟΓτ ^ τΡίατ General Example 3 Η Pmar ~ iTPta below &amp; below eyes) tm \ 1 ¢ 1 mCor fixed IT limit below fT 隈 α lower it comparative example 2 Γτ? ΟΓτ ~ Ding Lu below the T limit ^ lower eye α Comparative Example 3 hF limit below the fixed #T limit α lower Γτ? ΠΓτ ~ Comparative Example 4 ^ Where the lower limit is determined below the lower limit 10 minutes washing; &gt; Molybdenum _...-- . ^ .. M. ........ fife example 1 below the lower limit of quantification, the lower limit of the fixed mother, the lower limit of the lower limit, and the lower limit of the upper limit. Example 2 f lower limit of the lower limit, 歹 lower limit of the lower limit α, lower limit of the lower limit, example 3 Γτμτ ~ ίτ ^ ατ The ratio below the lower limit of setting <Example 1 SrnOTr ~ ΓτΙΟΓτ t The lower limit is lower than Comparative Example 2 The lower limit is hFraia lower than kFiita ^ The lower limit is lower than 3 The lower limit is lower than 3 ΓτΐΟΓτ The lower limit is lower than T Comparative Example 4 Fixed lower limit of fixed search Γτ? Ϊ «τ 1 day wash; &gt; Steel 媸 fife Example 1 Fixed ΐτι * ΐ · Α lower limit f lower limit taT ΐ Example 2 fixed + lower limit ατ ~ sfrmoT fixed f lower limit below Puro 3 fixed lower limit ατ fixed ¥ lower limit ^ ϊτι «ίατ ratio # 4 Example 1 4.1 9.7 fixed lower limit Comparative example 2 Fixed lower limit lower than IT lower limit Fixed lower limit lower than Comparative Example 3 Fixed lower limit lower than τ Limit lower fixed limit below PfFOTt ~ Comparative Example 4 fixed lower limit lower limit α lower than fixed lower limit ΓΠ * Γατ ~ 3 days wash ; &gt; Steel suspicion of cargo 1 Order below T limit, set an odd scream "down below f lower limit fife example 2 set f lower limit" down limit It limit to τ set f below minimum limit Example 3 set the agency lower limit "under lower limit Set lower limit w ifcUW 1 12 40 4.9 Comparative Example 2 Set 1 lower limit below 5.7 Set lower limit below Comparative Example 3 2.5 ii Set Iτ limit below Comparative Example 4 Set child lower limit below 3.8 Set ¥ lower limit below 7 days wash broadcast f Example 1 Lower limit of fixed mother α lower 5.8 Lower limit of yellow lower u lower t Example 2 ΊΛ 3.2 Lower limit of fixed lower α α Example 3 33 3.5 Determine itHifi 1 30 89 12 Comparative Example 2 5.8 18 Fixed mother T limit is T 3 8.3 20 3.0 Comparative Example 4 6 11 4.3 1, 8X 109 atom / cm2) 3. 2 X 109 a tom / cm2) 2. 0 X 109 atom / cm2) Limits 珉) Lower and lower -1iΙ- The application of the fixed example 2 ^ 11.1 1 page 15 4484 75 V. Description of the invention (12) In the same cleaning device of Example 1, cations are introduced between the supply outlet to the cleaning tank and the membrane filter for removing 0.1 Am particles in the branch piping inside the washing machine that supplies ultrapure water to the cleaning tank 5. The absorbing membrane module 'is regarded as an ion absorbing membrane module 20, and ultra-pure water is filtered and processed with the module 20 in its entirety, and is introduced into the washing tank 5. First, a wafer having a crystal surface manufactured by the 8-inch diameter pulling method (cz) with an η-type (100) and an impedance of 8 to 12 Ω · cm is subjected to a cleaning tank 1 Wash with ozone ultrapure water to wash with dilute fluoric acid in the washing tank 4. Secondly, the cleaning time of the ultrapure water performed in the cleaning tank 5 is changed by 10 minutes, 1 day, 3 days, and 7 days, and the cleaning β is performed to dry the silicon wafer after the cleaning is completed. A total reflection fluorescent X-ray analyzer was used to measure the amount of so-called metal impurities such as copper, iron, and nickel in the attached impurities, and the results are shown in Table 1. (Embodiment 3) In the same cleaning device as in Embodiment 1, the ultra-pure water is supplied to the branch pipe inside the washing machine of the% tank 5, and the supply to the cleaning tank is provided with 0.1 &quot; in A membrane module having a chelation angle is introduced between the membrane filters for fine particle removal, and used as an ion-adsorption membrane module 20, and the module 20 is used to completely filter and treat ultrapure water, and then introduce it into the washing Slot 5. And 乂 / 2 is a crystal manufactured by the 8-inch diameter drawing method (CZ): =. 0) and the 5th wafer with an impedance of 8 ~ 12 Ω · cro, follow the line, and wash the odorous milk of ultra pure water until it is washed.

4484 75 V. Description of the invention (13) Secondly, the washing time of the ultrapure water applied to the washing tank 5 is changed by 10 minutes, 1 day, 3 days, and 7 days, and the washing is performed. After the washing was finished, the Shixi wafer was dried and the amount of so-called metal impurities such as steel, iron, and nickel in the attached impurities was measured by a total reflection glare X-ray analyzer, and the results are shown in Table 1. (Comparative Example 1) In the same cleaning apparatus as in Example 1, ultrapure water was supplied without introducing the ion-adsorption membrane module 20. First, a silicon wafer made of a 8-inch diameter cz method with a surface of 1! Type (100) and an impedance of 8 to 12 Ω. 施 will be cleaned by °° The ozone ultrapure water in the tank 1 is washed until the diluted hydrofluoric acid in the tank 4 is washed. Next, the washing time of the ultrapure water performed in the washing tank 5 was changed by 100 minutes, 1 day, 3 days, and 7 days, and the washing was performed. After the washing was completed, the silicon wafer was dried, and the total amount of impurities such as copper, iron, and nickel called metal impurities was measured with a total reflection fluorescent X-ray analysis device. Table 1 shows the results. ', (Comparative example 2) In the same cleaning device as in Example 1, an anion absorbing membrane module was introduced into a branch pipe supplying ultrapure water to the washing tank 5 and a pipe outside the washing machine. The ion absorbing membrane module 20 was used, and ultra pure water was completely filtered and processed by the module 20, and then introduced into the washing tank 5. First, a silicon wafer made by an 8-inch diameter pulling method (cz) with a n-type (100) crystal surface and an impedance of 8 to 12 Ω, cm will be borrowed.

Page 17 4484 7 5 V. Description of the invention (14) From the washing of ozone ultrapure water in washing tank 1 to the washing with dilute hydrofluoric acid in washing tank 4. Secondly, the washing time of the ultrapure water performed in the washing tank 5 is changed by 10 minutes, 1 day, 3 days, and 7 days, and the washing is performed. After the washing was completed, the silicon wafer was dried, and the total amount of so-called metal impurities of copper, iron, and nickel in the attached impurities was measured by a total reflection fluorescent X-ray analysis device, and the results are shown in Table 1. (Comparative Example 3) In the same cleaning apparatus as in Example 1, a cation adsorption membrane module was introduced into a branch pipe supplying ultrapure water to the washing tank 5 and a pipe outside the washing machine was used as ions. The membrane module 20 is sucked, and ultra-pure water is completely processed by the module 20, and is introduced into the washing tank 5. First, a silicon wafer with a crystal surface manufactured by the 8-inch diameter pulling method (cz) with an η-type (100) and an impedance of 8 to 12 Ω · cm is subjected to a cleaning tank. The ozone ultrapure water of 1 is washed to the diluted hydrofluoric acid in the washing tank 4. Next, the washing time of the ultrapure water performed in the washing tank 5 was changed by 10 minutes, 1 day, 3 days, and 7 days, and washing was performed. After the washing was completed, the silicon wafer was dried, and the total reflection fluorescent X-ray analysis was used to measure the amount of copper, iron, and nickel called metal impurities in the attached impurities'. The results are shown in Table 1. (Comparative Example 4) In the same cleaning crack as in Example 1, it was sequestered in the branch pipe supplying ultrapure water to the washing tank 5 and introduced into the pipe outside the washing machine.

Page 18 4484 7 5

The membrane module was used as an ion-adsorbing membrane module 20, and Wang Ye used this model to filter and treat ultrapure water, and introduced it into the washing tank 5. First, the Shi Xi wafer manufactured by the 8-inch diameter pull method (cz) (type ⑴0) and with an impedance of 8 to 12 Ω _ will be subjected to the y method to wash the ozone of tank 1 The washing time of pure water is changed to the time of washing the ultrapure water in the washing tank 5 by the second of the dilute acid in the washing tank 4. The time is changed by 0 minutes, 1 day, 3 days, 7 days. While performing cleansing. After the washing was completed, the silicon wafer was dried, and the total amount of copper, iron, and nickel called metal impurities in the attached impurities was measured using a total reflection fluorescence X-ray analysis device. Table 1 shows the results. '(Example 4) A mixing tank 8 is provided in the cleaning tank 2 and a proper and necessary medicine is supplied to the mixing tank 8 from a measurement tank 10 containing interfacial active fluoric acid and a hydrogen peroxide measurement tank 丨 丨 mixing The finished medicine is transferred from the washing tank 8 to the washing tank 2. The washing tank 4 is provided with a mixing tank 9 ', and appropriate and necessary medicines are supplied from the gas acid measuring tank 12 to the mixing tank 9, and the mixed medicines are transferred from the washing tank 9 to the washing tank 4. The ultrapure water was supplied from the ultrapure water pipe 7 to the washing tank 5 reams, and the dissolved oxygen concentration in the ultrapure water was 2 / zg / L, and the dissolved hydrogen concentration was 1 mg / L. In the branch piping that supplies ultrapure water to the inside of the washing machine of the washing tank 5, an anion absorbing membrane module is introduced between the supply outlet to the washing tank and the membrane filter for removing particles of 0.1 m. 'As an ion absorbing membrane module 20, and using this module 20 to filter and treat ultrapure water in full amount, and introduce it into the washing tank

Page 19 4484 7 5 V. Description of the invention (16) 5 ° First, the crystal surface manufactured by the 8 inch diameter pulling method (cz) is η-type (100) and the resistivity is 8 ~ 12 Ω The .cm silicon wafer is cleaned from the ozone ultrapure water in the cleaning tank 1 to the dilute fluoric acid in the cleaning tank 4. Next, the washing time of the ultrapure water performed in the washing tank 5 was changed by 10 minutes, 1 day, 3 days, and 7 days, and the washing was performed. After the washing was completed, the silicon wafer was dried, and the total amount of so-called metal impurities such as copper, iron, and nickel in the attached impurities was measured by a total reflection fluorescent X-ray analysis device, and the results are shown in Table 2.

(Table 2) Coffee Zina washed dill 1 Molybdenum 1 逋 1 year Example 4 fixed 1 rF limit α lower house 1 lower rF limit lower than fixed mother lower limit Η FttOTf ~~ FtICot fixed ^ lower rna general example 6 a ΐ 叱] ^ 下 | «(L to T« &gt; * -i πι «ιατ Set the following comparative example i: 5 h7 limited to τ Ftpiut, set 1U minutes, wash 1 nickel, apply Price j4 Set the order below the T limit. Set the lower limit. The fixed lower limit. Set the It limit to set the mailing limit. To implement the T limit below the implementation of Example 6. 疋 ΐ The lower limit is less than the weight. The lower limit is T. The weight is below the T limit. 1 i 2U 6.4 Full bearing below the T limit 1 1 day wash 1 1 1 I m pf Example 4 Set the order below the lower limit f and set the lower limit ΤΤία lower Sfi 5 Set | lower limit lower 1 1 ^ lower limit α lower limit | lower limit a ® 6 The lower limit is set to τ! The lower limit is set to lower than the lower limit. 5 32 1_____iMJ 2.77 1 丨 7 Big wash 1 Nickel IT Example 4 The lower limit of the order ατ The lower limit of quantitative limit The lower limit of t and the lower limit of cesium i) 11 5.2疋 f 下 (¾f following examples) fixed scene below fixed lower limit α lower fixed lower than lower; comparative example 5 74 21 6.3 fixed f lower of steel: 1.8X10 9atom / cm2) Dingman's difficulty with iron: 3.2X109at〇m / cm3) Dingman's rotation with dart: 2.0X 109 atom / cm, p. 20 4484 75 V. Description of the invention (17) (Example 5) at In the same cleaning device as in Example 4, the branch piping inside the washing machine that supplies ultrapure water to the washing tank 5 is between the supply outlet to the washing tank and the 0.1 microparticle removal membrane filter. The cation-adsorption membrane module 'is introduced as the ion-adsorption membrane module 20', and the ultra-pure water is completely treated by this module 20, and is introduced into the washing tank 5. First, a silicon wafer with a crystal surface of π type (100) and an impedance of 8 to 12 Ω. Wash with ozone ultrapure water to wash with dilute fluoric acid in the washing tank 4. Next, the washing time of the ultrapure water performed in the washing tank 5 is changed by 10 minutes, 1 day, 3 days, and 7 days, and the washing is performed. After the washing was completed, the wafer was dried and the total reflection fluorescent X-ray analysis was used to determine the amount of copper and iron'nickel metal impurities in the attached impurities. The results are shown in Table 2 » (Example 6) In the same cleaning device as in Example 4, in the branch piping inside the washing machine that supplies ultrapure water to the washing tank 5, the supply outlet to the washing tank and the 0.1 microparticle removal film A che module having a chelate-forming group is introduced between the filters as the ion-adsorption membrane module 20, and ultra-pure water is completely filtered and processed with the module 20, and then introduced into the washing tank 5. First, a silicon wafer having a crystal surface of η-type (100) and an impedance of 8 to 12 Ω · cm manufactured by the 8-diameter diameter pulling method (cz) is subjected to a cleaning tank. Washing of ozone 1 ultrapure water to the

Page 21 4484 75 V. Description of the invention (18) Wash. Next, the washing time of the ultrapure water performed in the washing tank 5 is changed by J 0 minutes, 1 day, 3 days, and 7 days, and the washing is performed. After the washing was completed, the silicon wafer was dried, and the total amount of copper, iron, and nickel as impurities contained in the attached impurities was measured by a total reflection fluorescent X-ray analysis device, and the results are shown in Table 2. (Comparative Example 5) In the same cleaning apparatus as in Example 4, ultrapure water was supplied without introducing the ion absorbing membrane module 20. First of all, a Shi Xi wafer with a crystal surface manufactured by the 8-inch diameter pulling method (cz) is η-shaped (100) and the resistivity is 8 to 12 Ω · cm. The wafer is cleaned by Wash the ozone ultrapure water in tank 1 until the washing with dilute fluoric acid in tank 4 &gt; Next, 'wash the ultrapure water in the cleaning tank 5 in 10 minutes, Washing was performed after 1 day, 3 days, and 7 days. After the washing was completed, the silicon wafer was dried, and the total amount of copper, iron, and so-called metal impurities in the attached impurities were measured by a total reflection fluorescent X-ray analysis device, and the results are shown in Table 2. (Embodiment 7) FIG. 3 is a diagram showing a room-temperature fishery cleaning device consisting of five processes. In the cleaning tank 1, the cleaning is performed by ozone ultrapure water, and the cleaning is performed. In the tank 2, a surfactant is added to a mixed solution of hydrofluoric acid and hydrogen peroxide ', and the ultrasonic wave is washed. In the washing tank 3, washing with ozone ultrapure water is performed, and

Page 22 4484 7 5 V. Description of the invention (19) The clean tank 4 is treated with dilute fluorine, and washed with ultrapure water. Water is supplied to the washing tank 1 and the washing tank 3, and is supplied through the pipe 13 to be mixed and dissolved in the pipe, and further becomes inside. And in the cleaning tank 5, the "implementation of the last" is used to supply the ozone generated by the ultrapure odor mill 6 from the ultrapure water pipe 7, and the ozone ultrapure water is supplied to the cleaning tank.

The mixing tank 8 is misplaced, and the necessary and necessary medicines are supplied from the sealed tank 10 containing the interfacial active plutonium and the peroxidation disorder measuring tank u to the mixing A tank 8 ′, and the medicines after the mixing are transferred from the cleaning tank 8 to wash. = Tank 4 is provided with a mixing tank 9, and the metering tank 12 of the gas acid is transferred to the washing tank 4 when necessary mixing is completed to the mixing tank 9 '. Ultrapure water is supplied from the ultrapure water pipe 7 to the washing tank 5, and the dissolved oxygen concentration in the ultrapure water is 2 eg / L. An anion absorbing membrane module is introduced into the branch piping inside the washing machine that supplies ultrapure water to the washing tank 5 between the supply outlet to the washing tank and the membrane filter for fine particle removal. Ion-adsorption membrane module 20, and then, a hydrogen-dissolved membrane module 19 using a hollow wire of polyolefin is introduced. First, the crystal surface manufactured by the 8-inch diameter pulling method (cz) is η-shaped. (100) Dream wafers with an impedance ratio of 8 to 12 Ω · cm, from washing with ozone ultrapure water in washing tank 1 to washing with dilute fluoric acid in washing tank 8 Next ' The washing time of the ultrapure water performed in the washing tank 5 was changed by 10 minutes, 1 day, 3 days, and 7 days, and washing was performed.

4484 7 5 V. Description of the invention (20) After cleaning, the silicon wafer is dried, and the total reflection fluorescent X-ray analysis device is used to measure the amount of so-called metal impurities such as copper, iron, and nickel in the attached impurities. The results are shown in Table 3. F (unit: X 10satom / cm3) of copper attached to the silicon crystal® Before washing 1 4Ά Remove f Example 7 F lower limit lower than f lower limit lower than P8L lower f 以下 Example 8 f lower limit The difference is less than the lower limit and the lower limit is f. Example 9 Defining | mTor ~ Defining fTi * taT Defining the lower limit and ΛComparative example 6 Defering i Ft 1 * 6. Ατ ~ Defining the Itpsl and the lower limit are 10 points # 洗 _ίϊ__. ......... 1 silver baby! F gives 7 sets 1 sets the lower limit to T sets fT limits below ίξΐ t sets the lower limit of wealth _ | 8 fixed limits ατ sets the lower limit α to set | ΓτΤΓατ ~ 9 ^ fTFtiUT sets It is less than FtTlot ~ £ 20 minutes. 6 20 6.4 ^ Under «1 or less 丨 1 big wash; &gt; 1 媸 丨 Apply 1 Ϊ Γ Example 7 Below the lower limit of Dingxi 1 Lower limit α lower S fixed | lower Ft lower than f ~ Below the F limit ^ FMLa Lower ii Γ Mask Example 9 The following instructions are given below: The following instructions are given below! F under 6 ta! 10 owe 1 ΓΤΡΕατ ~ 丨 wash in 3 days! Molybdenum 1 鎞 i ϊ: 1 application Example 7 Defining the lower limit of f 3.2 Defining the lower limit of t 1 αi ¥ i 1 Fine 8 Defining the lower limit of f 3.2 Defining the lower limit α lower 1 1 Example 9 The lower limit of the signature is determined by lowering the lower limit of T. 1 6 10 33 1 4. ^ 1 丨 7 big cleansing 1 1 platinum 丽 f 丽 7 ^ lower limit 3.2 below f lower limit ^^ · \ 8 Ϊ * lower below 3.2 fixed lower limit FtfOTt ~ lower than lower limit mother Comparative example below the lower limit of foot 6 6 1 10 33 4.9 (Table 3) Lower mark of steel fixed: 1.8X109 atom / cm2) Lower limit of fixed steel of iron UXl09atom / ctn2) Selected fixed card: 2.0Xl09atom / cm25 (Implementation Example 8) In the same cleaning apparatus as in Example 7, a cation absorbing membrane module was introduced as an ion absorbing membrane module 20, and then a hydrogen-dissolving membrane module 19 using polyolefin hollow wires was introduced. ^ '

Page 24 4484 7 5 V. Description of the invention (21) Add hydrogen to the hydrogen dissolving membrane module to make the hydrogen dissolving concentration 1mg / L. First, a silicon wafer having a crystal surface manufactured by the 8-inch diameter pull method (cz) is η-type (100) and has an impedance of 8 to 12 Ω · cm. The ozone ultrapure water of 1 is washed to the diluted hydrofluoric acid in the washing tank 4. Next, the washing time of the ultrapure water performed in the washing tank 5 was changed by 10 minutes, 1 day, 3 days, and 7 days, and the washing was performed. After the washing was completed, the Shixi wafer was dried, and the total amount of copper, iron, and nickel, which are so-called metallic impurities, in the attached impurities were measured by a total reflection X-ray analysis device, and the results are shown in Table 3. (Example 9) In the same cleaning apparatus as in Example 7, a hydrazone module having a chelate-forming group was introduced as an ion-adsorbing membrane module 20, and then hydrogen dissolution using a hollow wire using polyolefin was introduced. Membrane module 1 9. Add argon to the hydrogen dissolving membrane module to make the hydrogen dissolving concentration 1mg / L. First, a silicon wafer with a crystal surface manufactured by the 8-inch diameter pulling method (cz) that is η-shaped (100) and resistivity is 8 to 1 2 Ω · cm. Wash the ozone ultrapure water in the cleaning tank 1 to the dilute hydrofluoric acid in the cleaning tank 4. Next, the washing time of the ultrapure water performed in the washing tank 5 was changed by 10 minutes, 1 day, 3 days, and 7 days, and washing was performed. After the cleaning process is completed, the silicon wafer is dried,

P.25 4484 7 5 V. Description of the invention (22) An analytical device is used to measure the amount of so-called metal impurities of copper, iron, and nickel in the attached impurities, and the results are shown in Table 3. (Comparative Example 6) In the same cleaning apparatus as in Example 7, the piping supplied to the cleaning tank 5 was not provided with an ion absorbing membrane ', and a gas-soluble membrane module 19 using a hollow wire of polyolefin was introduced. Add air to the hydrogen dissolving membrane module so that the hydrogen dissolving concentration is 1 mg / L. First, a Shi Xi wafer with a crystal surface manufactured by the 8-inch diameter pulling method (cz) with an η-type (100) and an impedance of 8 to 12 Q .cm is subjected to a cleaning bath. The ozone ultrapure water of 1 is washed to the washing of the dilute acid in the washing tank 4. Next, the washing time of the ultrapure water performed in the washing tank 5 was changed by 100 minutes, 1 day, and 3 days to 7 days, and washing was performed. After the washing was finished, the Shixi wafer was dried, and the total amount of copper, iron, and nickel so-called metal impurities in the attached impurities were measured by a total reflection fluorescent X-ray analysis device. The results are shown in Table 3. (Embodiment 10) Figure 4 shows a room-temperature wet cleaning device composed of five processes. In the washing tank 1, washing with ultrapure water of stinky odor is performed, and the washing tank is used. In step 2, a surfactant is added to a mixed solution of hydrofluoric acid and hydrogen peroxide, and then ultrasonic cleaning is performed. In the washing tank 3, washing with ozone ultrapure water is performed. In the washing tank 4, a dilute hydrofluoric acid treatment is performed, and in the washing tank 5, the final

Page 4484 7 5

V. Description of the invention (23) Ultra-pure water is washed in the washing tank 1 and the washing solution 3, and is supplied through the pipe 13 to be mixed and dissolved in the pipe, and then becomes inside. 'The ozone generated by the ultrapure odor generator 6 is supplied from the ultrapure water pipe 7 and the ozone ultrapure water is supplied to the cleaning tank. The cleaning tank 2 is provided with a mixing tank 8 and contains the amount of interfacial active fluoric acid. The tank 10 and the hydrogen peroxide metering tank n donor price 11 supply appropriate and necessary medicines to the mixing tank 8, and the mixed medicines are transferred from the washing tank 8 to the washing tank 2. A mixing tank 9 is provided in the washing tank 4, and appropriate and necessary medicines are supplied to the mixing tank 9 from the metering tank 12 of hydrofluoric acid, and the finished medicines are transferred from the washing tank 9 to the washing tank 4. The ultrapure water is supplied from the ultrapure water pipe 7 to the washing tank 5, and the dissolved oxygen concentration in the ultrapure water is 2 μg / L. Into the branch piping inside the washing machine that supplies ultrapure water to the washing tank 5, a cation adsorption membrane module 20 is introduced between the supply outlet to the washing tank and the 0.1 microparticle removal membrane filter, and then, The anion absorbing membrane module 21 is introduced, and the ultrapure water is completely filtered by these modules, and then introduced into the washing tank 5. Using this washer, a MOS diode with a gate oxide film thickness (4.5 nm) was fabricated. The element area is 1 X l (T4ciii2 'judging the current value is 1 X 1 〇-4A, and the dielectric breakdown characteristic test of the MOS diode is performed, and the average value of the dielectric breakdown voltage of the component (number of components 1 0 〇) is investigated. The results are shown in Table 4.

Page 27 4484 75 V. Description of the invention (24) Table 4 MOS Dipole 艚 (element # 10 a flat 岣) when the edge of the edge of the special buckle-(Seven Qi l: MV / αη ϋ Example of ten cases of real cesium Eleven real running cases, twelve poor cases + three real spore cases, fourteen insulation damage, field service. Report: 4 gas 12.0 A 12.2 12.3 12.2 10.4 None # 面 葙: lXlCHcm2 Judging current value: 1 × 10 · + Α (Implementation Example 11) In the same device as in Example 10, in the branch piping inside the washing machine that supplies ultrapure water to the washing tank 5, a supply outlet to the washing tank and a film for removing particles of 0.1 yin An integrated absorbing membrane module 20 is introduced between the filters, and then an anion absorbing membrane module 21 is introduced, and the ultrapure water is completely filtered by these modules and introduced into the washing tank 5. Use This washer was used to make a MOS diode with a gate oxide film thickness (4.5 nm). With an element area of 1 X 10-4 cm2, the current value was determined to be 1 X 1, and the insulation of the MOS diode was performed. Failure characteristics test 'and the results of investigating the average value of the dielectric breakdown voltage of the device (number of components 100) are shown in Table 4. (Example 12) Yu and Shi Example 10: The same device introduces anions into the branch piping inside the washing machine that supplies ultrapure water to the washing tank 5 between the supply outlet to the washing tank and the membrane filter for removing 0.1 μm particles. The sorption membrane module 20 is then introduced, and the chelated sorption membrane module _2 1 is introduced.

4484 75 V. Description of the invention (25) The whole amount of pure water is filtered and introduced into the washing tank 5. Using this washer ', an M 0 S diode with a gate oxide film thickness (4.5 nm) was produced. A device with an area of 1 × 10 cm2 and a current value of 1 ′ was used to perform an insulation failure characteristic test of the pole body. The results of investigating the average value of the insulation failure voltage of the components (number of components 100) are shown in Table 4. ° (Thirteenth embodiment) In the same device as in the tenth embodiment, 'in the branch piping inside the washing machine that supplies ultrapure water to the washing tank 5', the supply outlet to the washing tank and 0.1 ym particles A cationic adsorption membrane module 20 is introduced between the removal membrane filters, and then a chelated adsorption membrane module 21 is introduced, and the ultrapure water is completely filtered by these modules, and introduced into the washing tank 5 . Using this washer ', a MOS diode with a gate oxide film thickness (4.5 nm) was fabricated. A device with an area of 1 x 1 0 4 cm 2 and a current value of 1 X 1 0_4A 'was used to perform an insulation failure characteristic test of the MOS diode, and the result of investigating the average value of the insulation failure voltage of the device (number of components 100) Shown in Table 4. (Embodiment 14) In the same device as Embodiment 10, in the branch piping inside the washing machine that supplies ultrapure water to the washing tank 5, the supply outlet to the washing tank and 0.1 &quot; m Only the anion absorbing membrane module 2 0 ′ is introduced between the membrane filters for fine particle removal, and these modules are used to filter the entire amount of ultrapure water into the washing

Page 29

Claims (1)

4484 7 5 VI. Application for Patent Scope 1. A wet cleaning device that supplies ultrapure water to a use point inside the device through piping, and uses ultrapure water as a washing liquid to perform cleaning, which is characterized by : A module is provided in the middle of the piping inside the device, and the module is filled with a porous membrane that holds a polymer chain having an anion exchange group, a cation exchange group, or a chelate-forming group inside the membrane. 2. The wet cleaning device according to item 1 of the scope of the patent application, wherein the cleaning liquid is hydrogen-containing ultrapure water containing hydrogen. 3. The wet cleaning device according to item 2 of the patent application scope, wherein the hydrogen adding device is disposed downstream of the above module. 4. The wet cleaning device according to item 2 of the scope of patent application, which makes the hydrogen adding device upstream of the above module. 5. The wet cleaning device according to item 1 of the scope of the patent application, wherein the module filled with a porous membrane holding a polymer chain having an anion exchange group, and the module filled with porous holding a polymer chain having a cation exchange group At least two of the module of the membrane and the module filled with a porous membrane holding a polymer chain having a chelate-forming group are provided in combination. 6 · The wet cleaning device described in item 1 of the scope of patent application, The above washing is the last washing.